Curable composition

ABSTRACT

A curable composition, useful as a thermosetting binder, having a polycarboxy polymer or co-polymer, an emulsion polymer, and a multifunctional polyol.

This invention relates to a formaldehyde-free curable aqueous composition and its use as a binder for heat-resistant nonwovens.

Nonwoven fabrics are composed of fibers which may be consolidated by purely mechanical means such as, for example, by entanglement caused by needle-punching, by an air-laid process, and by a wet-laid process; by chemical means such as, for example, treatment with a polymeric binder; or by a combination of mechanical and chemical means before, during, or after nonwoven fabric formation. Binders for non-woven materials have mostly contained resins, such as formaldehyde condensate resins that include urea-formaldehyde (UF), phenol-formaldehyde (PF), and melamine-formaldehyde (MF). However, formaldehyde is a known carcinogen, so users of formaldehyde containing resins are looking for less harmful alternatives. Further, such resins tend to yellow when submitted to high temperatures.

Some nonwoven fabrics are used at temperatures substantially higher than ambient temperature such as, for example, glass fiber-containing nonwoven fabrics which are impregnated with a hot asphaltic composition pursuant to making roofing shingles or roll roofing material. When a nonwoven fabric is contacted with a hot asphaltic composition at temperatures of 150-250° C. the nonwoven fabric may sag, shrink, or otherwise become distorted. Therefore, nonwoven fabrics which incorporate a curable aqueous composition should substantially retain the properties contributed by the cured aqueous composition such as, for example, dimensional stability. In addition, the cured composition should not substantially detract from essential nonwoven fabric characteristics, as would be the case, for example, if the cured composition were too rigid or brittle or became sticky under processing conditions.

Curable compositions containing little or no formaldehyde are highly desirable in a variety of products, due to the health and environmental problems associated with formaldehyde. Existing commercial formaldehyde-free binders contain a carboxylic acid polymer and a polyol that esterify and form a thermoset when heat cured. Some applications, for example, as used in bonding glass matts, require both heat resistance and a greater degree of flexibility of the end product. Commercial formaldehyde-free binders have been blended with other polymers, as described, for example, in International Publication No. WO 2006/063802 A2. However, the dispersions described therein are high Tg systems that would be unsuitable for applications requiring both flexibility and strength of the product. Moreover, the systems based on amine-containing polyols are susceptible to undesirable high temperature discoloration. On the other hand, systems based on known amine-free polyols, such as glycerol or sorbitol, show better high temperature color stability properties but poor wet strength properties. Thus, there is a need for new formaldehyde-free binders for making a heat-resistant nonwoven fabric with improved flexibility, improved wet strength and a reduced tendency to discolor.

This invention is a curable aqueous composition comprising (a) at least one polycarboxy (co)polymer comprising at least two carboxylic acid groups, anhydride groups, or salts thereof; (b) polymer particles of at least one emulsion (co)polymer having a glass transition temperature, Tg, of less than 80° C., as determined by the Fox equation; (c) at least one polyol of the formula

where X is selected from O or C; and

when X is O:

-   -   o and p are each 0, and R₇ and R₈ do not exist;     -   R₁ and R₂ are independently in each instance selected from         alkyl, alkylene, oxyalkylene, alkoxy and hydroxyalkyl;     -   R₅ and R₆ are independently in each instance selected from H,         hydroxy, alkyl, alkoxy and hydroxyalkyl;     -   and m, n, and q are integers selected independently from 1 to 5;     -   such that the total number of hydroxyl groups is between 4 and         8;

when X is C:

-   -   m, n, o, and p are integers selected independently from 1 to 16;     -   R₁, R₂, R₃ and R₄ are independently in each instance selected         from alkylene, oxyalkylene and alkoxy;     -   R₅, R₆, R₇ and R₈ are independently in each instance selected         from H, alkyl, hydroxyalkyl and hydroxy;     -   and q=1;     -   such that the total number of hydroxyl groups is between 4 and         8;     -   and wherein in each case of X is either O or C the ratio of the         number of equivalents of said carboxylic acid groups, anhydride         groups, or salts thereof to the number of equivalents of said         hydroxyl groups is from 1/0.01 to 1/3.

Preferably, the ratio of equivalents of the carboxy groups in the polycarboxy polymer or copolymer to the hydroxy groups in the polyol is from 1/0.02 to 1/2, more preferably from 1/0.1 to 1/1.5, still more preferably from 1/0.1 to 1/0.8. By “independently in each instance selected from” we mean to include the fact that, for example, when m is greater than one, the several R₁ groups involved can be the same or different and selected in each instance from the substituents described above. Thus, in each instance where there might be a multiple of each of R₁, R₂ (etc), in each selection of each one of the multiple, the selection can be different or the same.

The composition provides a formaldehyde-free binder useful for making heat resistant nonwovens with improved flexibility, improved wet strength and a reduced tendency to discolor when compared to compositions utilizing amine-containing polyols.

This invention also is a method for treating substrates with such a composition, which includes forming a curable aqueous composition comprising admixing the components of the invention with water or one or more aqueous solvent; contacting said substrate with the curable aqueous composition or, alternatively, applying the curable aqueous composition to the substrate; and heating the curable aqueous composition at a temperature of from 100° C. to 400° C. The invention also provides a fibrous article, non-woven article or composite prepared by the method for treating substrates with the composition, as described above.

Preferably, the emulsion (co)polymer of component (b) of the curable aqueous composition has a glass transition temperature, Tg, of less than 50° C., as determined by the Fox equation.

Preferably, the polymer particles of the at least one emulsion (co)polymer (b) are stabilized with acid-functional monomers and have a titratable acid content of 0.2-5.0%.

Preferably, the polycarboxy (co)polymer (a) of the curable aqueous composition is an addition polymer or copolymer comprising at least one copolymerized ethylenically unsaturated carboxylic acid-containing monomer.

Preferably, the polyol (c) of the curable aqueous composition is selected from the group consisting of diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, pentaerythritol, dipentaerythritol, ditrimethylolpropane, 1 to 15-propoxylated pentaerythritol, 1 to 15-ethoxylated pentaerythritol, 1 to 15-propoxylated ditrimethylolpropane, 1 to 15-ethoxylated ditrimethylolpropane, 1-15-ethoxylated dipentaerythritol, 1-15-propoxylated dipentaerythritol, and mixtures thereof.

In one embodiment, the curable aqueous composition further comprises one or more polyols selected from the group consisting of glycerol, ethyleneglycol, diethyleneglycol, triethyleneglycol, hexanediol, trimethylolpropane, sorbitol, sucrose, and glucose.

In another embodiment, the emulsion (co)polymer of the curable aqueous composition is present in an amount of from 1% to 50%, by weight based on the sum of the weight of the polycarboxy (co)polymer (a) and the weight of the polyol (c), all weights being taken on a solids basis. In yet another embodiment, the curable aqueous composition further comprises a phosphorous-containing accelerator such as those disclosed in U.S. Pat. No. 5,661,213.

The invention also encompasses the curable aqueous composition comprising the components (a), (b) and (c) as described above, wherein the at least one polyol (c) of the formula I is as described above, and specifically for the case where X is C and m, n, o, and p are integers selected independently from 2 to 16.

When we refer to “(co)polymer” we refer to either a homopolymer or copolymer, or both of them in combination. We use the term “(meth)acrylate” to refer to either acrylate or methacrylate and the term “(meth)acrylic” refers to either acrylic or methacrylic.

As used herein, the term “polycarboxy (co)polymer” is an oligomer, co-oligomer, polymer or copolymer with at least two carboxylic acid functional groups, anhydride groups, or salts thereof.

As used herein, the term “acid-functional monomer” refers to ethylenically unsaturated monomers containing acid groups or their salts. This includes monomers containing carboxylic acid groups.

As used herein, the term “hydroxyalkyl” may refer to one, or more than one, hydroxyl group attached to an alkyl group, which may or may not be branched.

As used herein, the term “oxyalkylene” refers to units having the structure: —(O-A)-, where O-A represents the monomeric residual of the polymerization reaction product of alkylene oxides, as well as the 1-carbon homolog oxymethylene, —(OCH₂)—. Examples of oxyalkylenes include, but are not limited to: oxyethylene with the structure —(OCH₂CH₂)—; and oxypropylene with the structure —(OC₃H₆)—.

Referring to Figure I: R₁ (and R₂, R₃ and R₄) can be branched units, and can be connected to other R₁ (and R₂, R₃ and R₄, respectively) units, terminating in one or more R₅ (and R₆, R₈ and R₇, respectively) units.

“Glass transition temperature” or “T_(g)” is the glass transition temperature, of a copolymer calculated with the Fox equation [Bulletin of the American Physical Society 1, 3 Page 123 (1956)] as follows:

$\frac{1}{T_{g}} = {\frac{w_{1}}{T_{g{(1)}}} + \frac{w_{2}}{T_{g{(2)}}}}$

For a copolymer, w₁ and w₂ refer to the weight fraction of the two comonomers, based on weight of monomers charged to the reaction vessel, and T_(g(1)) and T_(g(2)) refer to the glass transition temperatures of the two corresponding homopolymers in degrees Kelvin. For polymers containing three or more monomers, additional terms are added (w_(n)/T_(g(n))). The glass transition temperatures of homopolymers for the purposes of this invention are those reported in “Polymer Handbook”, edited by J. Brandrup and E. H. Immergut, Interscience Publishers, 1966, unless that publication does not report the Tg of a particular homopolymer, in which case the Tg of the homopolymer is measured by differential scanning colorimetry (DSC). To measure the glass transition temperature of a homopolymer by DSC, the homopolymer sample is prepared and maintained in the absence of ammonia or primary amine. The homopolymer sample is dried, preheated to 120° C., rapidly cooled to −100° C., and then heated to 150° C., at a rate of 20° C./minute while data is collected. The glass transition temperature for the homopolymer is measured at the midpoint of the inflection using the half-height method.

The Fox calculation of the T_(g) for a copolymer containing crosslinking monomers as polymerized units, is based on glass transition temperatures for the homopolymers formed from each crosslinking monomer wherein the homopolymer is not in the presence of ammonia or a primary amine. The glass transition temperature values for homopolymers formed from the anionic monomers are for anionic homopolymers in the acid form.

For the case in which the emulsion (co)polymer particles are made up of two or more mutually incompatible (co)polymers, the Tg is calculated for each (co)polymer phase according to the component monomers present in each (co)polymer.

The preferred polyol (c) is pentaerythritol. Other preferred polyols (c) are polyglycerols with an —OH functionality between 4 and 8. Specifically, these are diglycerol (functionality 4), triglycerol (functionality 5), tetraglycerol (functionality 6), pentaglycerol (functionality 7), hexaglycerol (functionality 8), and mixtures thereof. Of these, the triglycerol is particularly preferred. However, other amine-free polyols (c) can be used. Amine-containing polyols, such as triethanolamine (TEOA), are less desirable in this application because they suffer from discoloration when submitted to high temperatures. The polyol preferably should be sufficiently nonvolatile that it will substantially remain available for reaction with the polycarboxy (co)polymer in the composition during heating and curing operations. Other polyols (c) include compounds with a molecular weight less than about 10,000 bearing at least four hydroxyl groups such as, for example, ditrimethylolpropane, ethoxylated (or propoxylated) pentaerythritols, and ethoxylated (or propoxylated) dipentaerythritols, etc. Ethoxylated (EO) or propoxylated (PO) pentaerythritol (shown below), may have multiple oxyalkylene groups (oxyethylene or oxypropylene units, respectively) as R₉ groups (w, x, y, and z can be integers, for example 1-15; and w, x, y, and z are not necessarily the same):

Additionally, one skilled in the art could envisage such polyols with mixed oxyalkylene groups. Thus, some R₉ units could be oxyethylene units, while others could be oxypropylene units, either located in separate R₉ chains, or within the same R₉ chain. Also envisaged are cases for which one or more of w, x, y and z are greater than 15. Similar considerations are applicable to the other ethoxylated or propoxylated polyols described above.

Although less preferred, other oligo-glycerols and polyglycerols can function adequately.

The formaldehyde-free curable aqueous composition contains a polycarboxy (co)polymer. The polycarboxy (co)polymer must be sufficiently nonvolatile that it will substantially remain available for reaction with the polyol in the composition during heating and curing operations. The polycarboxy (co)polymer may be, for example, a polyester containing at least two carboxylic acid groups; alternatively, it may be an addition polymer or oligomer containing at least two copolymerized carboxylic acid-functional monomers. The polycarboxy (co)polymer is preferably an addition polymer formed from at least one ethylenically unsaturated monomer. In one embodiment of the invention, the curable copolymer composition is a solid composition such as, for example, a powder or a film. The solid composition may be obtained by various methods of drying, such as, for example spray drying, fluidized bed drying, freeze drying, and the like.

In a preferred embodiment, the curable (co)polymer composition is a curable aqueous composition. “Aqueous” as used herein includes water, and mixtures of water and water-miscible solvents. In this embodiment, the polycarboxy (co)polymer (a) may be in the form of a solution of the addition polymer in an aqueous medium such as, for example, a polyacrylic acid homopolymer or an alkali-soluble resin which has been solubilized in a basic medium.

The polycarboxy (co)polymer must contain at least two carboxylic acid groups, anhydride groups, or salts thereof. Ethylenically unsaturated carboxylic acids such as, for example, methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, α,β-methylene glutaric acid, monoalkyl maleates, and monoalkyl fumarates; ethylenically unsaturated anhydrides such as, for example, maleic anhydride, itaconic anhydride, acrylic anhydride, and methacrylic anhydride; and salts thereof, at a level of from about 1% to 100%, by weight, based on the weight of the addition polymer, may be used. Additional ethylenically unsaturated monomer may include ethylenically-unsaturated nonionic acrylic monomers, for example, (meth)acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl methacrylate; hydroxyalkyl(meth)acrylate monomers such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate; phosphoalkyl (meth)acrylates such as phosphoethyl (meth)acrylate, phosphopropyl (meth)acrylate, and phosphobutyl (meth)acrylate, phosphodialkyl (meth)acrylates; as well as phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl crotonates, and allyl phosphate.

Other ethylenically-unsaturated nonionic monomers which may be incorporated into the polycarboxy (co)polymer include vinylaromatic compounds, such as styrene, α-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, vinyltoluenes, and the like; vinyl acetate, vinyl butyrate and other vinyl esters; vinyl monomers such as vinyl alcohol, vinyl chloride, vinyl toluene, vinyl benzophenone, and vinylidene chloride.

Further ethylenically-unsaturated nonionic acrylic monomers include acrylamides and alkyl-substituted acrylamides, such as acrylamide, methacrylamide, N-tert-butylacrylamide and N-methyl(meth)acrylamide; hydroxyl-substituted acrylamides, such as methylolacrylamide, and beta-hydroxyalkylamides; acrylonitrile or methacrylonitrile; and the like.

When the polycarboxy (co)polymer is in the form of a solution of the addition polymer in an aqueous medium such as, for example, a polyacrylic acid homopolymer or an alkali-soluble resin which has been solubilized in a basic medium, the weight average molecular weight may be from about 300 to about 10,000,000. Preferred is a molecular weight from about 1000 to about 250,000.

In one embodiment of the present invention, the polycarboxy addition (co)polymers may be oligomers or co-oligomers of ethylenically-unsaturated carboxylic acids prepared by free radical addition polymerization, having a number average molecular weight of from 300 to 1000900.

In one preferred embodiment, the polycarboxy (co)polymer is a polyacrylic acid homopolymer (pAA) for which a weight average molecular weight of no greater than 10,000, is suitable, more preferably no greater than 5,000, even more preferably no greater than 3,000, and with 2,000-3,000 being advantageous.

When the addition polymer is an alkali-soluble resin having a carboxylic acid, anhydride, or salt thereof, content of from about 5% to about 30%, by weight based on the total weight of the addition polymer, a molecular weight from about 1,000 to about 100,000 is preferred (with from 1,000 to about 20,000 being more preferred), since higher molecular weight alkali-soluble resins lead to curable compositions exhibiting excessive viscosity.

Polycarboxy (co)polymer molecular weights reported herein, unless otherwise indicated, are weight average molecular weights, Mw, as measured by gel permeation chromatography (GPC) using polystyrene standards as is known in the art. However, number average molecular weights, Mn, may be considered to be more meaningful at low molecular weights for which Mw is about 1,000 or less. In such cases, GPC measurements can still be used, although polyacrylic acid standards may be more suitable for calibration purposes. For aqueous solutions, such as the homopolymer polyacrylic acid (pAA) mentioned above, the GPC standard is a polyacrylic acid standard, as is generally used in the art.

The formaldehyde-free curable aqueous composition of this invention may optionally contain a phosphorous-containing cure accelerator which may be a compound with a molecular weight less than about 1000 such as, for example, an alkali metal hypophosphite salt, hypophosphorous acid, an alkali metal phosphite, an alkali metal polyphosphate, an alkali metal dihydrogen phosphate, a polyphosphoric acid, and an alkyl phosphinic acid or it can be an oligomer or polymer bearing phosphorous-containing groups such as, for example, an addition polymer of acrylic and/or maleic acid formed in the presence of sodium hypophosphite (SHP), addition polymers such as, for example, the copolymer of the present invention prepared from ethylenically-unsaturated monomers in the presence of phosphorous salt chain transfer agents or terminators, and addition polymers containing acid-functional monomer residues such as, for example, copolymerized phosphoethyl methacrylate, and like phosphonic acid esters. Copolymerized vinyl sulfonic acid monomers, and their salts can function similarly. The phosphorous-containing species can be used at a level of from 0% to 40%, preferably from 0% to 20%, further preferably from 0% to 15%, more preferably from 0% to 10% by weight based on the combined weight of the polycarboxy (co)polymer and the polyol. We prefer a level of phosphorous-containing accelerator of from about 2.5% to about 10%, by weight based on the combined weight of the polycarboxy (co)polymer and the polyol.

Thus, a particularly preferred curable thermoset composition utilizes a polyacrylic acid homopolymer of 2,500 weight average molecular weight in combination with pentaerythritol, such that the ratio of carboxy groups to —OH groups is 1.0/0.3, in conjunction with 5% SHP as a phosphorous containing catalyst.

In addition, if a phosphorous-containing chain transfer agent is used to polymerize the polycarboxy (co)polymer employed in the curable composition of this invention, the phosphorous-terminated (co)polymer can act as a phosphorous-containing cure accelerator as defined herein. Specifically, the addition polymer may be formed in the presence of phosphorous-containing chain transfer agents such as, for example, hypophosphorous acid and its salts, as is disclosed in U.S. Pat. Nos. 5,077,361 and 5,294,686, which are hereby incorporated herein by reference, so as to incorporate the phosphorous-containing accelerator and the polycarboxy component in the same molecule. The polymerization reaction to prepare such a phosphorous-containing (co)polymer is otherwise similar to that used to prepare other polycarboxy (co)polymers, as described herein below.

The formaldehyde-free curable aqueous composition may be prepared by admixing the polycarboxy (co)polymer, the polyol, and, optionally, the phosphorous-containing accelerator using conventional mixing techniques. In another embodiment a carboxyl- or anhydride-containing addition (co)polymer and an hydroxy-functional monomer may be present in the same addition (co)polymer, which addition (co)polymer would contain both the carboxyl, anhydride, or salts thereof functionality and the hydroxyl functionality. In another embodiment the phosphorous-containing accelerator may be present in the polycarboxy addition (co)polymer, which addition (co)polymer may be mixed with the polyol (b). In yet another embodiment, the carboxyl- or anhydride-containing addition (co)polymer, the hydroxy-functional monomer, and the phosphorous-containing accelerator may be present in the same addition (co)polymer. Other embodiments will be apparent to one skilled in the art.

In a preferred embodiment of this invention, the curable binder composition contains a strong acid. “Strong acid” means a non-carboxylic acid having at least one pKa of no greater than 3. In this embodiment, the curable binder composition preferably contains from 0.01 to 0.2 equivalents of a strong acid, relative to the equivalents of total carboxylic acid, more preferably from 0.01 to 0.18 equivalents. “Total carboxylic acid” means the entire amount of the carboxylic acid present in the (co)polymer composition. The strong acid may be a mineral acid, such as, for example, sulfuric acid, or an organic acid, such as, for example a sulfonic acid. Mineral acids are preferred.

Preferably, the pH of the aqueous curable composition is less than 3.5, also preferably less than 2.5, which pH will depend, among other things, on the choice of polyol or adjuvants that may be employed, and the strength and amount of any strong acid or base that may be added.

In one embodiment of the invention, the curable composition further contains at least one low molecular weight polybasic carboxylic acid, anhydride or salt thereof having a molecular weight of 1000 or less, preferably 500 or less, and most preferably 200 or less. “Polybasic” means having at least two reactive acid or anhydride functional groups (see, for example, Hawley's Condensed Chemical Dictionary, 14^(th) Ed., 2002, John Wiley and Sons, Inc.). Examples of suitable low molecular weight polybasic carboxylic acids and anhydrides include, for example, maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, sebacic acid, azelaic acid, adipic acid, citric acid, glutaric acid, tartaric acid, itaconic acid, trimellitic acid, hemimellitic acid, trimesic acid, tricarballytic acid, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, oligomers of carboxylic acid, and the like. Optionally, the low molecular weight polybasic carboxylic acid, anhydride or salt thereof may be mixed with the hydroxyl-containing compound, under reactive conditions, prior to mixing with the polycarboxy (co)polymer. As discussed above, in certain embodiments, the (co)polymer composition can include an accelerator. The accelerator may be present during this reaction, which can be an in-situ reaction, or alternatively, the accelerator may be added to the composition after completion of this in-situ reaction and prior to mixing with the polycarboxy (co)polymer.

The polycarboxy (co)polymer may be prepared by free radical addition polymerization. In the embodiment of the invention where the composition is in the form of a solid, the (co)polymer can be prepared, for example, in a hot tube, either in the absence of solvent or with low levels of solvent for reduced viscosity. In other embodiments of the invention, the (co)polymer can be prepared by solution polymerization, emulsion polymerization, or suspension polymerization techniques for polymerizing ethylenically-unsaturated monomers, which are well known in the art.

The polymerization reaction to prepare the polycarboxy (co)polymer composition can be initiated by various methods known in the art such as, for example, by using the thermal decomposition of an initiator and by using an oxidation-reduction reaction (“redox reaction”) to generate free radicals to effect the polymerization. The polycarboxy (co)polymer composition can be prepared in water or in solvent/water mixtures such as, for example, i-propanol/water, tetrahydrofuran/water, and dioxane/water.

Chain transfer agents such as mercaptans, polymercaptans, and halogen compounds can be used in the polymerization mixture in order to moderate the molecular weight of the polycarboxy (co)polymer composition. Generally, from 0% to 10% by weight, based on the weight of the polymeric binder, of C₄-C₂₀ alkyl mercaptans, mercaptopropionic acid, or esters of mercaptopropionic acid, can be used. Similarly, as stated above, in another embodiment the polycarboxy (co)polymer composition can be formed in the presence of phosphorous-containing chain transfer agents such as, for example, hypophosphorous acid and its salts, so as to incorporate a phosphorous-containing species in the polymer backbone.

The carboxyl groups of the polycarboxy (co)polymer composition may be neutralized with a base. The base may be added before, during, or after polymerization of monomers to form the polycarboxy (co)polymer composition. The neutralization may at least partially occur prior to, or while treating a substrate.

In one embodiment of the invention, the carboxyl groups of the polycarboxy (co)polymer composition may be neutralized with a fixed base, meaning a base which is substantially non-volatile under the conditions of the treatment such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, or t-butylammonium hydroxide. The fixed base must be sufficiently nonvolatile that it will substantially remain in the composition during heating and curing operations.

In a different embodiment of the invention, the carboxy groups may be neutralized with a volatile base, meaning a base which is substantially volatile under the conditions of treatment of the substrate with the copolymer composition. Suitable volatile bases for neutralization include, for example, ammonia or volatile lower alkyl amines. The volatile base can be used in addition to the fixed base. Fixed multivalent bases such as, for example, calcium carbonate can tend to destabilize an aqueous dispersion, if the polycarboxy (co)polymer composition is used in the form of an aqueous dispersion, but can be used in minor amount.

The formaldehyde-free curable aqueous composition is a substantially thermoplastic, or substantially uncrosslinked, composition when it is applied to the substrate, although low levels of deliberate or adventitious crosslinking may be present.

The curable binder composition is blended with an emulsion polymer including, as polymerized units, at least one copolymerized ethylenically-unsaturated nonionic acrylic monomer. “Emulsion polymer”, or “emulsion (co)polymer”, means a (co)polymer dispersed in an aqueous medium that has been prepared by emulsion polymerization techniques known in the art as is discussed in detail in D. C. Blackley, Emulsion Polymerization (Wiley, 1975) and also in H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 2 (Ernest Benn Ltd., London 1972). By “nonionic monomer” herein is meant that the copolymerized monomer residue does not bear any substantial ionic charge between pH=1-14. The emulsion polymer used in blending is separate and different from the polycarboxy (co)polymer of the binder of this invention in the case when the polycarboxy (co)polymer is also an emulsion, and may be used in blending with the curable binder composition of the invention. The emulsion polymer used in blending may be present in an amount of from 1% to 50%, or from 1% to 40%, preferably from 1% to 30%, more preferably from 1.5% to 20%, and still more preferably 5% to 15%, by weight based on the weight of the curable binder composition, on a solids basis. It is particularly advantageous that the cured thermoset composition has both flexibility and strength. The emulsion polymer used in blending preferably has a Tg of less than 80° C., more preferably less than 50° C., even more preferably less than 40° C., and also advantageously less than 25° C., or even less than 0° C.

Thus, a particularly advantageous embodiment of the invention provides a blend composition comprising an emulsion polymer and a curable thermoset composition utilizing a polyacrylic acid homopolymer of 2,500 weight average molecular weight in combination with pentaerythritol, such that the ratio of carboxy groups to —OH groups is 1.0/0.3, in conjunction with 5% SHP as a phosphorous containing catalyst, wherein the emulsion polymer used in blending has a Tg less than 80° C., more preferably less than 50° C., and is present in an amount of 10% by weight based on the weight of the curable binder composition, on a solids basis.

Another particularly advantageous embodiment of the invention provides a blend composition comprising an emulsion polymer and a curable thermoset composition utilizing a polyacrylic acid homopolymer of 2,500 weight average molecular weight in combination with pentaerythritol and glycerol, such that the ratio of carboxy groups to —OH groups is 1.0/0.3, in conjunction with 5% SHP as a phosphorous containing catalyst, wherein the emulsion polymer used in blending has a Tg less than 80° C., more preferably less than 50° C., and is present in an amount of 10% by weight based on the weight of the curable binder composition, on a solids basis.

Other preferred embodiments of the invention provide blend compositions comprising an emulsion polymer and a curable thermoset composition utilizing the polycarboxy (co)polymers described above, and particularly the polyacrylic acid homopolymers, in combination with at least one polyol (c) selected from the group consisting of diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, pentaerythritol, dipentaerythritol, ditrimethylolpropane, 1 to 15-propoxylated pentaerythritol, 1 to 15-ethoxylated pentaerythritol, 1 to 15-propoxylated ditrimethylolpropane, 1 to 15-ethoxylated ditrimethylolpropane, 1-15-ethoxylated dipentaerythritol, and 1-15-propoxylated dipentaerythritol. Preferably, the emulsion polymer used in blending has a Tg less than 80° C., more preferably less than 50° C., and is present in an amount of from 5% to 10%, by weight based on the weight of the curable binder composition, on a solids basis. These blend compositions optionally comprise a phosphorous-containing accelerator.

The ethylenically-unsaturated nonionic acrylic monomers of the emulsion polymer used in blending may include, for example, (meth)acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl methacrylate; hydroxyalkyl(meth)acrylate monomers such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate. Other ethylenically-unsaturated nonionic monomers which may be incorporated into the polymer include vinylaromatic compounds, such as styrene, α-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, vinyltoluenes, and the like; vinyl acetate, vinyl butyrate and other vinyl esters; vinyl monomers such as vinyl alcohol, vinyl-chloride, vinyl toluene, vinyl benzophenone, and vinylidene chloride.

Further ethylenically-unsaturated nonionic acrylic monomers include acrylamides and alkyl-substituted acrylamides, such as acrylamide, methacrylamide, N-tert-butylacrylamide and N-methyl(meth)acrylamide; hydroxyl-substituted acrylamides, such as methylolacrylamide, and beta-hydroxyalkylamides; as well as acrylonitrile and methacrylonitrile.

The emulsion polymer used in blending with the curable binder composition of this invention may contain one or more monoethylenically-unsaturated acid monomer, such as, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 1-allyloxy-2-hydroxypropane sulfonic acid, alkyl allyl sulfosuccinic acid, sulfoethyl (meth)acrylate, phosphoalkyl (meth)acrylates such as phosphoethyl (meth)acrylate, phosphopropyl (meth)acrylate, and phosphobutyl (meth)acrylate, phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl (meth)acrylates, phosphodialkyl crotonates, and allyl phosphate. Preferably, the emulsion polymer used in blending has a titratable acid content less than 5% in order to avoid imparting undesirable water sensitivity to the composition. In one preferred embodiment the emulsion (co)polymer is stabilized with one or more acid-functional monomer and has a titratable acid content of 0.2-5.0%. Titratable acid content is readily determined using automated instruments, such as the TitraLab TIM900 auto titrator (Radiometer analytical SAS, Lyon, France), and methodologies known in the art (see Example 8). The method determines the amount of base (potassium hydroxide) required to neutralize the accessible acid in a known quantity of emulsion polymer of known solids content. The titration results then allow calculation of the amount of acid available in the serum phase of the latex and on the surface of the particles. This can be expressed as a percentage of emulsion polymer solids, and this percentage is the titratable acid content.

Anionic or nonionic surfactants, or mixtures thereof, can be used in the emulsion polymerization. For some applications, such as those requiring resistance to water sensitivity, the use of polymerizable surfactants (also known as reactive surfactants) can be advantageous; these surfactants are known in the art, as described, for example, in U.S. Patent Publication No. 2003/0149119 or U.S. Patent Publication No. 2001/0031826. The polymerization can be carried out by various means such as, for example, with all of the monomers added to the reaction kettle prior to beginning the polymerization reaction, with a portion of the ethylenically-unsaturated monomer in emulsified form present in the reaction kettle at the beginning of the polymerization reaction, or with a small particle size emulsion polymer seed present in the reaction kettle at the beginning of the polymerization reaction.

The polymerization reaction to prepare the emulsion (co)polymer can be initiated by various methods known in the art such as, for example, by using the thermal decomposition of an initiator and by using an oxidation-reduction reaction (“redox reaction”) to generate free radicals to effect the polymerization. The emulsion (co)polymer can be prepared in water or in solvent/water mixtures such as, for example, i-propanol/water, tetrahydrofuran/water, and dioxane/water.

Chain transfer agents such as mercaptans, polymercaptans, and halogen compounds can be used in the polymerization mixture in order to moderate the molecular weight of the polycarboxy (co)polymer composition. Generally, from 0% to 10% by weight, based on the weight of the polymeric binder, of C₄-C₂₀ alkyl mercaptans, mercaptopropionic acid, or esters of mercaptopropionic acid, can be used.

The emulsion polymer used in blending with the curable binder composition of this invention may contain copolymerized multi-ethylenically-unsaturated monomers such as, for example, allyl methacrylate, diallyl phthalate, 1,4-butylene glycol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, butadiene, and divinyl benzene.

The emulsion (co)polymer particles can be made up of two or more mutually incompatible (co)polymers. These mutually incompatible (co)polymers can be present in various morphological configurations such as, for example, core/shell particles, core/shell particles with shell phases incompletely encapsulating the core, core/shell particles with a multiplicity of cores, interpenetrating network particles, and the like. In such cases, the Tg of at least one of the phases has a Tg of less than 80° C., more preferably less than 50° C., even more preferably less than 40° C., and also advantageously less than 25° C., or even less than 0° C. In one embodiment of the invention, and also for applications for which enhanced waterproofing properties are desired of the curable composition, the emulsion polymer(s) used in blending with the curable binder composition of this invention is a predominately hydrophobic emulsion polymer including, as polymerized units, greater than 30%, preferably greater than 40%, more preferably greater than 50%, and even more preferably greater than 60%, by weight, based on the weight of the emulsion polymer solids, of an ethylenically-unsaturated acrylic monomer including a C₅ or greater alkyl group. This approach to waterproofing has been disclosed in U.S. Patent Publication No. 20050048212A1. “Acrylic monomer including a C₅ or greater alkyl group” means an acrylic monomer bearing an aliphatic alkyl group having five or more C atoms, the alkyl group including n-alkyl, s-alkyl, i-alkyl, and t-alkyl groups. Suitable ethylenically-unsaturated monomers including a C₅ or greater alkyl group include (C₅-C₃₀) alkyl esters of (meth)acrylic acid, such as amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate; unsaturated vinyl esters of (meth)acrylic acid such as those derived from fatty acids and fatty alcohols; surfactant monomers including long chain alkoxy- or alkylphenoxy(polyalkylene oxide) (meth)acrylates, such as C₁₈H₃₇-(ethylene oxide)₂₀ methacrylate and C₁₂H₂₅-(ethylene oxide)₂₃ methacrylate; N-alkyl substituted (meth)acrylamides such as octyl acrylamide; and the like. The monomer including a C₅ or greater alkyl group can also contain functionality, such as amido, aldehyde, ureido, polyether and the like, but preferably does not contain an acid or hydroxy group. Emulsion polymers containing such monomers can be prepared by emulsion polymerization, preferably by the method for forming polymers of U.S. Pat. No. 5,521,266. A surfactant may be added to the emulsion polymer before or during the blending of the emulsion polymer with the copolymer composition. Preferably, the surfactant is added in the amount of from 0.5% to 20%, preferably from 2% to 10%, by weight, based on the weight of emulsion polymer solids. Preferred is a surfactant having a HLB value of greater than 15.

The predominately hydrophobic emulsion polymer can also include, as copolymerized units, up to 10%, preferably up to 5%, by weight based on the weight of the emulsion polymer solids, monomer bearing a carboxylic acid group, anhydride group, or salt thereof or hydroxyl-group, such as (meth)acrylic acid and hydroxyethyl(meth)acrylate. In this embodiment, the hydrophobic emulsion polymer may be present in an amount of from 1% to 40%, preferably from 1% to 30%, more preferably from 1.5% to 15%, and more preferably 5% to 10%, by weight based on the weight of the curable binder composition, on a solids basis.

The weight average particle diameter of the emulsion (co)polymer particles used in blending can be from 80 nanometers to 1000 nanometers, as measured using a Brookhaven BI-90 Particle Sizer. However, polymodal particle size distributions such as those disclosed in U.S. Pat. Nos. 4,384,056 and 4,539,361, hereby incorporated herein by reference, can be employed.

The blend composition of this invention can contain, in addition, conventional treatment components such as, for example, emulsifiers; pigments; fillers or extenders; anti-migration aids; curing agents; coalescents; surfactants, particularly nonionic surfactants; spreading agents; mineral oil dust suppressing agents; biocides; plasticizers; organosilanes; anti-foaming agents such as dimethicones, silicone oils and ethoxylated nonionics; corrosion inhibitors, particularly corrosion inhibitors effective at pH<4 such as thioureas, oxalates, and chromates; colorants; antistatic agents; lubricants; waxes; anti-oxidants; coupling agents such as silanes, particularly Silquest™ A-187 (manufactured by GE Silicones—OSi Specialties, located in Wilton, Conn., USA); Wetlink Silanes from GE (e.g Wetlink 78), and Dynasylan™ silanes from Degussa particularly, epoxy silanes such as, but not limited to, Dynasylan™ GLYMO and GLYEO; and oligomeric silanes such as HYDROSIL™. Also, polymers not of the present invention; and waterproofing agents such as silicones and emulsion polymers, particularly hydrophobic emulsion polymers containing, as copolymerized units, greater than 30% by weight, based on the weight of the emulsion polymer solids, ethylenically-unsaturated acrylic monomer containing a C5 or greater alkyl group.

The blend composition of this invention is preferably formaldehyde-free. “Formaldehyde-free” means that the composition is substantially free from formaldehyde, nor does it liberate substantial formaldehyde as a result of drying and/or curing. To minimize the formaldehyde content of the (co)polymer composition it is preferred, when preparing a polymer of the present invention, to use polymerization adjuncts such as, for example, initiators, reducing agents, chain transfer agents, biocides, surfactants, and the like, which are themselves free from formaldehyde, do not generate formaldehyde during the polymerization process, and do not generate or emit formaldehyde during the treatment of a substrate. Likewise, it is preferable that any formulation additives be similarly formaldehyde free. “Substantially free from formaldehyde” means that when low levels of formaldehyde are acceptable in the waterborne composition or when compelling reasons exist for using adjuncts which generate or emit formaldehyde, substantially formaldehyde-free waterborne compositions can be used.

The blend composition of this invention may be used for treating various substrates. Such treatments can be commonly described as, for example, coating, sizing, saturating, bonding, combinations thereof, and the like. Typical substrates include wood, including, for example, solid wood, wood particles, fibers, chips, flour, pulp, and flakes; metal; plastic; fibers such as polyester, glass fibers; woven and non-woven fabrics; and the like and their composite fibers. The (co)polymer blend composition can be applied to a substrate by conventional techniques such as, for example, air or airless spraying, padding, saturating, roll coating, foam coating, curtain coating, beater deposition, coagulation, or the like.

In one embodiment of this invention, the blend composition can be used as a binder for heat-resistant non-woven fabrics such as, for example, non-wovens which contain heat-resistant fibers such as, for example, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, certain polyester fibers, rayon fibers, rock wool, and glass fibers. “Heat-resistant fibers” mean fibers which are substantially unaffected by exposure to temperatures above 125° C. Heat-resistant non-wovens can also contain fibers which are not in themselves heat-resistant such as, for example, certain polyester fibers, rayon fibers, nylon fibers, and super-absorbent fibers, in so far as they do not materially adversely affect the performance of the substrate.

As discussed above, non-woven fabrics incorporating a (co)polymer blend composition should substantially retain the properties contributed by the cured aqueous composition such as, for example, tensile strength, and not substantially detract from essential non-woven fabric characteristics. The cured composition should not be too rigid or brittle, or become sticky under processing conditions.

The curable aqueous (co)polymer blend composition, after it is applied to a substrate, is heated to effect drying and curing. The duration and temperature of heating will affect the rate of drying, processability, handleability; and property development of the treated substrate. Heat treatment at from 120° C. to 400° C. for a period of time between from 3 seconds to 15 minutes can be carried out; treatment at from 175° C. to 225° C. is preferred. “Curing” means a chemical or morphological change which is sufficient to alter the properties of the (co)polymer blend composition such as, for example, via covalent chemical reaction, ionic interaction or clustering, improved adhesion to the substrate, phase transformation or inversion, hydrogen bonding, and the like. The drying and curing functions can be performed in two or more distinct steps, if desired. For example, the blend composition can be first heated at a temperature and for a time sufficient to substantially dry but not to substantially cure the composition, and then heated for a second time at a higher temperature and/or for a longer period of time to effect curing. Such a procedure, referred to as “B-staging,” can be used to provide binder-treated nonwoven, for example, in roll form, which can at a later stage be cured, with or without forming or molding into a particular configuration, concurrent with the curing process.

The heat-resistant non-wovens can be used for applications such as, for example, insulation batts or rolls, as reinforcing mat for roofing or flooring applications, as roving, as microglass-based substrate for printed circuit boards or battery separators, as filter stock (e.g. for air duct filters), as tape stock, and as reinforcement scrim in cementitious and non-cementitious coatings for masonry, in ceiling tiles, cellulosic roofing tiles, window treatments, wall coverings, molded parts, for curly pulp modification, for powder coating, and the like.

The non yellowing flexible binders of the invention are also useful for bonding wood chips, abrasive matts, decorative laminate paper, laminating adhesives, filtration paper, or cotton rag bonding for automotive sound insulation.

EXAMPLES Example 1 Synthesis of Polycarboxy Solution Polymer

The polymer produced with this procedure was used in the examples in Table 1 below. To a three liter four-neck flask equipped with a mechanical stirrer, a condenser, a nitrogen sweep, a thermometer and inlets for the gradual additions of monomer, initiator and sodium hypophosphite solutions, was added 710 grams of deionized water. A chain regulator stock solution was prepared by dissolving 1250 grams of sodium hypophosphite monohydrate in 1528 grams of deionized water. A total of 243.2 grams was removed from the stock solution and half (121.6) of this solution was added to the water charge and heated to 93° C. The remaining half of the chain regulator solution was used as co-feed solution. A monomer charge of 1216 grams of glacial acrylic acid was prepared. An initiator solution was prepared by dissolving 12.16 grams of sodium persulfate in 30.7 grams of DI water.

The acrylic acid, sodium persulfate and sodium hypophosphite (SHP) charges were added linearly and separately over two hours to the stirring water charge. Temperature was maintained at 93°±1° C.

The resultant polymer solution was allowed to cool to room temperature and diluted with 274 grams of deionized water. The solution had a solids content of 52.7%, pH of 3.2, viscosity of 210 centipoises (measured on a Brookfield LVF viscometer, #4 spindle at 100 rpm) and residual monomer content of less than 0.01%. The weight average (Mw) molecular weight by gel permeation chromatography (GPC, using a polyacrylic acid standard for calibration) was 2456, or, approximately 2500.

Example 2 Aqueous Curable Thermoset Compositions Polycarboxy Solution Polymer+Multifunctional Polyols

A series of aqueous curable thermoset compositions were prepared using the polyacrylic acid polymer (pAA) of Example 1 along with each of the following multifunctional polyols:

Amine-Containing Polyols

Triethanolamine, functionality 3, (used in Thermoset Composition 1A)

Amine-Free Polyols

Glycerol, functionality 3, (used in Thermoset Composition 2A)

Diglycerol, functionality 4, (used in Thermoset Composition 3A)

Pentaerythritol, functionality 4, (used in Thermoset Composition 4A)

Sorbitol, functionality 6, (used in Thermoset Composition 5A)

The COOH/OH ratio of these curable thermosets was 1.0/0.5, except for the sample utilizing pentaerythritol for which the maximum level that could be dissolved in the system was used (1.0/0.3), and also sorbitol (also 1.0/0.3, for comparative purposes). Sodium hypophosphite (SHP) was used as a catalyst.

The aqueous curable thermoset compositions were prepared as follows: To 145.0 grams of polyacrylic acid of Example 1 (diluted to 50% solids; Mw=2500) was added 22.7 grams of glycerol (97% active), 8.1 grams of sodium hypophosphite solution (50% solids) and 24.2 grams of water. The pH of the mixture was 2.6 and the viscosity was 96.5 centipoises (measured on a Brookfield LVF viscometer, #4 spindle at 100 rpm). The active ingredients (components other than water) were 50.4%.

Prepared similarly, the compositions of the aqueous curable thermosets are presented in Table 1, below. Water was added to give solids of 50+/−1%.

TABLE 1 Composition of aqueous curable thermosets (grams): Thermoset pAA SHP COOH/ Composition Crosslinker (50% Solid) Crosslinker (50% Solid) OH Sample 1A Triethanolamine (98% active)¹ 132.5 26.3 7.2 1.0/0.5 Sample 2A Glycerol (97% active) 145.0 22.7 8.1 1.0/0.5 Sample 3A Diglycerol (100% active) 148.6 20.3 8.2 1.0/0.5 Sample 4A Pentaerythritol (100% solid) 162.2 11.0 13.5 1.0/0.3 Sample 5A Sorbitol (100% solid) 164.4 9.8 13.7 1.0/0.3 ¹also sulfuric acid (95%), approx. 10 g, post-added to neutralize to pH 3.0.

Example 3 Blends of the Aqueous Curable Thermosets with Emulsion Polymers

The above thermoset compositions were blended with emulsion polymers as shown below in Table 2 (90% thermoset with 10% emulsion polymer, solids on solids; the emulsion polymers were stabilized with 5% solids on solids of Tergitol™ 15S40, a nonionic surfactant available from The Dow Chemical Company, Midland, Mich., USA, before blending). The following emulsion polymers were used for blending:

(a) Primal™ E-357 EF 69 MMA/30 BA/0.9 MAA, (Titratable Acid Content: 0.48%) (b) Primal™ CM-219 EF 50 BA/47 Sty/2.9 MAA, (Titratable Acid Content: 0.76%)

(MMA is methyl methacrylate; BA is butyl acrylate; Sty is styrene; MAA is methacrylic acid). Primal™ E-357 EF emulsion and Primal™ CM-219 EF emulsion are both commercially available (Rohm and Haas Company, Philadelphia, USA).

TABLE 2 Composition of aqueous curable thermoset/emulsion polymer blends (grams): Blend Composition¹ Thermoset Emulsion Thermoset Emulsion Sample 1B(a) Thermoset Triethanolamine Primal E-357 EF 135.0 15.0 Sample 2B(a) Thermoset Glycerol Primal E-357 EF 135.0 15.0 Sample 3B(a) Thermoset Diglycerol Primal E-357 EF 135.0 15.0 Sample 4B(a) Thermoset Pentaerythritol Primal E-357 EF 135.0 15.0 Sample 4B(b) Thermoset Pentaerythritol Primal CM-219 EF 135.0 15.0 Sample 5B(b) Thermoset Sorbitol Primal CM-219 EF 135.0 15.0 ¹water, approx. 2.5 g, was added to each sample to maintain solids at 50%.

Example 4 Color Measurements of Cured Thermoset/Emulsion Polymer Blend Compositions

Color measurements were made in order to assess the extent of coloring that occurs upon heating for a period of 60 minutes at 200° C. The thermoset compositions were diluted to 20% solids and the samples were prepared by applying the dilute composition onto the GFA glass paper to give a dry weight of 40%+/−2% by weight binder add-on (dry binder weight as a percentage of filter paper weight) on the GFA paper. The GFA paper can be obtained from Whatman (Whatman International Ltd., Maidstone, England). The measurements were made using a portable spectrophotometer (spectro-guide from BYK-Gardner, Columbia, Md., USA) with a D65 illuminant (daylight) and an observer at 100, following a procedure that is well known throughout the coatings industry. See, for example, ASTM E1164. The cured thermoset/emulsion blends prepared utilizing the polyols (c) of structure I were compared with cured thermoset/emulsion blend compositions comprising an amine-containing polyol, Table 3. The b value represents the yellowing color. The delta b value (b for sample on the paper—b for the paper) represents the yellowing of the composition.

TABLE 3 Color measurements for cured thermoset/emulsion polymer blend compositions Blend Color Measurements Composition L a b delta b (Control) GFA paper 98.26 0.31 0.21 Sample 1B(a) E-357/Thermoset 94.03 −0.30 6.28 6.07 Triethanolamine Sample 2B(a) E-357/Thermoset 95.30 −0.03 1.51 1.30 Glycerol Sample 3B(a) E-357/Thermoset 95.21 −0.11 1.53 1.32 Diglycerol Sample 4B(a) E-357/Thermoset 95.21 −0.36 2.74 2.53 Pentaerythritol The color measurements are sometimes referred to as “L, a, b measurement” because the parameters recorded are L (lightness), a (+ red/− green) and b (+ yellow/− blue).

As the delta b value represents the yellowing of the compositions, it can be seen that the composition that utilizes an amine crosslinker shows a greater extent of the undesirable yellowing.

Example 5 Evaluation of Tensile Strength of Cured Thermoset/Emulsion Polymer Blend Compositions

In this example, the strength of the resulting cured thermoset/emulsion polymer blends as a function of the component multifunctional polyol was explored. The extent of effective crosslinking can be ascertained by comparing the wet tensile strength with the dry tensile strength.

The aqueous curable blend compositions of Table 2 were evaluated for wet and dry tensile strength as follows. Glass microfiber filter paper sheets (20.3×.25.4 cm, Cat No. 1820 866, Whatman International Ltd., Maidstone, England) were dipped in each sample binder composition and run through a roll padder with roll pressures of 45 psi. The coated sheets were then dried by heating at 90° C. for 5 minutes in a Mathis oven. Post drying weight was determined to calculate binder add-on (40%+/−2% by weight binder add-on, see above). Dried sheets were then cured in a Mathis oven at a temperature of 200° C. for 3 minutes.

The cured sheets were cut into 1 inch (cross machine direction) by 4 inch (machine direction) strips and tested for tensile strength in the machine direction in a Zwick 1120 tensile tester (Zwick Roell AG, Ulm, Germany). The fixture gap was 1 inch and the pull rate was 1 inch/minute. Strips were tested either “as is” (dry tensile) or immediately after 15 minutes in an autoclave at 112° C. and 1.5 bar (wet tensile). Tensile strengths were recorded as the peak force measured during parting (Table 4). Data reported are averages of 7 test strips for each binder composition tested.

TABLE 4 Tensile strength for cured thermoset/emulsion polymer blend compositions Tensile Blend Strength (Mpa) Composition Dry Wet Sample 2B(a) E-357 EF/Thermoset Glycerol 31.7 4.1 Sample 3B(a) E-357 EF/Thermoset Diglycerol 31.9 13.6 Sample 4B(b) CM-219 EF/Thermoset Pentaerythritol 37.2 13.5 Sample 5B(b) CM-219 EF/Thermoset Sorbitol 31.4 5.2

The inventive emulsion blends (Sample 3B(a) and Sample 4B(b)) utilizing thermosets with the polyols (c) of FIG. 1 have significantly higher wet tensile strengths than those of the comparative blends (Sample 2B(a) and Sample 5B(b)).

Example 6 Maximum Elongation of the Cured Thermoset/Emulsion Polymer Blend Compositions

A comparison was made of the flexibility of the cured thermoset/emulsion polymer blend versus that of the corresponding (non-blend) thermoset. The following emulsion polymers were used for blending:

(a) Primal ™ E-357 EF 69 MMA/30 BA/0.9 MAA, Tg ~ 37° C. (b) Primal ™ CM-219 EF 50 BA/47 Sty/2.9 MAA, Tg ~ 4° C. (c) Primal ™ E-3318 71.9 EA/23.9 MMA/4 AM, Tg ~ 5° C. (d) Primal ™ EP-6110 52.4 MMA/42.5 EA/5 MAM, Tg ~ 39° C. (e) Primal ™ B-85 ER 89.5 MMA/9.9 EA/0.4 MAA, Tg ~ 87° C. (MMA is methyl methacrylate; BA is butyl acrylate; MAA is methacrylic acid; Sty is styrene; EA is ethyl acrylate; AM is acrylamide; MAM is methyl acrylamide).

All of the emulsion polymers (a)-(e) are commercially available (Rohm and Haas Company, Philadelphia, USA). The emulsion polymers were blended with the thermoset composition of Sample 4A (thermoset pentaerythritol) in the manner described in Example 3, with the modifications noted in the Table below (Table 5).

Samples were prepared and evaluated for flexibility as follows. A spunbound needle-punched polyester substrate (150 g/m²) was dipped in each sample binder blend composition and run through a roll padder with roll pressures of 45 psi to obtain a binder add-on weight of 23%+/−2%. The coated substrate was then cured by heating at 200° C. for 3 minutes in a Mathis oven. The cured substrate was cut into 2 inch (cross machine direction) by 9 inch (machine direction) strips (1 mm thick) and tested for elongation in the machine direction in a MTS 1/M tensile tester (MTS systems, Eden Prairie, Minn., USA). The fixture gap was 7 inch and the pull rate was 4 inch/minute. The maximum elongations of the strips are shown below in Table 5.

TABLE 5 Maximum elongation for cured blend versus cured thermoset compositions Maximum Composition Elongation, % Sample 4A Thermoset Pentaerythritol 15.0 Sample 4B(b) CM-219 EF/Thermoset Pentaerythritol 56.0 Sample 4B(c) E-3318/Thermoset Pentaerythritol 40.0 Sample 4B(d) EP-6110/Thermoset Pentaerythritol 40.0 Sample 4B(e) B-58 ER/Thermoset Pentaerythritol 45.0 The emulsion polymer is present in the blend at 20% by weight (solids on solids), except for Sample 4B(b) where the CM-219 is present in the blend at 10% by weight (solids on solids).

Cured samples of the thermoset/emulsion polymer blend of the invention show improved flexibility, as measured by the maximum elongation, compared to the corresponding cured thermoset composition. The maximum elongation does not show a direct correlation with the Tg of the polymer in the blend.

Example 7 Elastic Domain Limit Force of Cured Thermoset/Emulsion Polymer Blend Compositions

The elastic domain limit force was determined for the cured thermoset/emulsion polymer blend compositions of Example 6. This force gives a measure of the resilience of the cured thermoset/emulsion polymer blends (Table 6).

TABLE 6 Maximum force of elastic domain for cured thermoset and cured thermoset/emulsion polymer blend compositions using different polymers in the blend Elastic Domain Composition Limit Force, N Sample 4A Thermoset Pentaerythritol 285.0 Sample 4B(b) CM-219 EF/Thermoset Pentaerythritol 240.0 Sample 4B(c) E-3318/Thermoset Pentaerythritol 223.0 Sample 4B(d) EP-6110/Thermoset Pentaerythritol 242.0 Sample 4B(e) B-58 ER/Thermoset Pentaerythritol 165.0 The emulsion polymer is present in the blend at 20% by weight (solids on solids), except for Sample 4B(b) where the CM-219 is present in the blend at 10% by weight (solids on solids).

Although all of the thermoset/polymer blends result in improved maximum elongation of the cured system (Example 6), it is found that high Tg polymers suffer from significantly lower elastic domain limit force. This means that cured thermoset/polymer blends using high Tg polymers will undergo irreversible deformation far more easily under end-use conditions that include any flexing or elongation of the product. On the other hand, the inventive blend compositions comprising the low Tg polymers used in the cured thermoset/polymer blends result in greater flexibility and strength in the final product and thus can recover their shape and integrity after applied physical stresses.

Example 8 Measurement of Total Solids By Weight

Where we have measured total solids by weight, we used the ASTM D-2369 method as follows.

Procedure:

-   1. Weigh aluminum dish to the 4th decimal place. Record this weight. -   2. Weigh out appropriately 0.5 grams of sample and record the weight     of the dish and sample to the 4th decimal place. Note that the     sample should be distributed over the dish surface: a few drops of     water can be used to aid in distributing the sample. Determination     should be done in duplicate. Place the sample in a 150° C. oven for     30 minutes. -   3. Remove the sample from the oven wearing leather gloves or with     tongs and allow to cool to room temperature in a constant     temperature and constant humidity room (25+/−3° C.; 50+/−5% relative     humidity) for approximately 2 minutes. -   4. Weigh and record the aluminum dish and polymer to the 4th decimal     place. -   5. Use the equations below to determine the percent solids (%     Solids):

Before Drying

(weight of dish and wet sample)−(weight of dish)=(weight of wet sample)

After Drying

(weight of dish and polymer)−(weight of dish)=(weight of polymer)

Then:

% Solids=100×(weight of polymer)/(weight of wet sample)

Example 9 Determination of Titratable Acid Content

Titratable acid was determined as follows, with the procedure being performed in triplicate for each emulsion polymer studied:

Note: appropriate caution and safety procedures should be employed when handling strong acids or strong bases, particularly, in this case, potassium hydroxide.

1. The emulsion polymer sample is first subjected to Strong Acid ion exchange resin, IRN 77 (Rohm and Haas Company, Philadelphia, Pa.), in the manner described below: 20 grams of the emulsion polymer latex are mixed with 10 grams of deionized water and 10 grams of IRN 77 for 30 minutes. The ion exchanged sample is then filtered through cheese cloth and the new solids level determined. Each titration sample is then weighed out (to 4 decimal places) to around 5 grams and diluted with 1M KCl solution. 2. The sample is then titrated with 0.5 N potassium hydroxide solution following the instrument procedure, generally as follows:

The potassium hydroxide titration procedure is selected from the TitraLab software. The auto titrator feed lines are flushed with 0.5 N potassium hydroxide to clear the lines of any air bubbles. The diluted ion exchanged latex sample is placed on the sample station and the electrode and stirrer are lowered into the sample. From the software menu, the option “run, current method” is selected in order to initiate the titration. The method locates multiple endpoints according to the pKa of the acid functionality types and environment. The instrument calculates the cumulative amount of potassium hydroxide added, the moles of potassium hydroxide added, and the milli-equivalents of acid titrated. The percent of titratable acid can be back calculated from the amount of sample loaded using known procedures. 

1. A curable aqueous composition comprising (a) at least one polycarboxy (co)polymer comprising at least two carboxylic acid groups, anhydride groups, or salts thereof; (b) polymer particles of at least one emulsion (co)polymer having a glass transition temperature, Tg, of less than 80° C., as determined by the Fox equation; (c) at least one polyol of the formula

where X is selected from O or C; and when X is O: o and p are each 0, and R₇ and R₈ do not exist; R₁ and R₂ are independently in each instance selected from alkyl, alkylene, oxyalkylene, alkoxy and hydroxyalkyl; R₅ and R₆ are independently in each instance selected from H, hydroxy, alkyl, alkoxy and hydroxyalkyl; and m, n, and q are integers selected independently from 1 to 5; such that the total number of hydroxyl groups is between 4 and 8; when X is C: m, n, o, and p are integers selected independently from 1 to 16; R₁, R₂, R₃ and R₄ are independently in each instance selected from alkylene, oxyalkylene and alkoxy; R₅, R₆, R₇ and R₈ are independently in each instance selected from H, alkyl, hydroxyalkyl and hydroxy; and q=1; such that the total number of hydroxyl groups is between 4 and 8; and wherein in each case of X is either O or C the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or salts thereof to the number of equivalents of said hydroxyl groups is from 1/0.01 to 1/3.
 2. The curable aqueous composition of claim 1 wherein the at least one emulsion (co)polymer (b) has a glass transition temperature, Tg, of less than 50° C., as determined by the Fox equation.
 3. The curable aqueous composition of claim 1 wherein the polycarboxy (co)polymer (a) is an addition polymer or copolymer comprising at least one copolymerized ethylenically unsaturated carboxylic acid-containing monomer.
 4. The curable aqueous composition of claim 1 wherein the polyol (c) is selected from the group consisting of diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, pentaerythritol, dipentaerythritol, ditrimethylolpropane, 1 to 15-propoxylated pentaerythritol, 1 to 15-ethoxylated pentaerythritol, 1 to 15-propoxylated ditrimethylolpropane, 1 to 15-ethoxylated ditrimethylolpropane, 1-15-ethoxylated dipentaerythritol, 1-15-propoxylated dipentaerythritol, and mixtures thereof.
 5. The curable aqueous composition of claim 1 further comprising one or more polyols selected from the group consisting of glycerol, ethyleneglycol, diethyleneglycol, triethyleneglycol, hexanediol, trimethylolpropane, sorbitol, sucrose, and glucose.
 6. The curable aqueous composition of claim 1 wherein the emulsion (co)polymer is present in an amount of from 1% to 50%, by weight based on the sum of the weight of the polycarboxy (co)polymer (a) and the weight of the polyol (c), all weights being taken on a solids basis.
 7. The curable aqueous composition of claim 1 further comprising a phosphorous-containing accelerator.
 8. A method for treating substrates comprising: forming a curable aqueous composition comprising admixing with water or one or more aqueous solvent (a) at least one polycarboxy (co)polymer comprising at least two carboxylic acid groups, anhydride groups, or salts thereof (b) polymer particles of at least one emulsion (co)polymer having a glass transition temperature, Tg, of less than 80° C., as determined by the Fox equation; (c) at least one polyol of the formula I.

where X is selected from O or C; and when X is O: o and p are each 0, and R₇ and R₈ do not exist; R₁ and R₂ are independently in each instance selected from alkyl, alkylene, oxyalkylene, alkoxy and hydroxyalkyl; R₅ and R₆ are independently in each instance selected from H, hydroxy, alkyl, alkoxy and hydroxyalkyl; and m, n, and q are integers selected independently from 1 to 5; such that the total number of hydroxyl groups is between 4 and 8; when X is C: m, n, o, and p are integers selected independently from 1 to 16; R₁, R₂, R₃ and R₄ are independently in each instance selected from alkylene, oxyalkylene and alkoxy; R₅, R₆, R₇ and R₈ are independently in each instance selected from H, alkyl, hydroxyalkyl and hydroxy; and q=1; such that the total number of hydroxyl groups is between 4 and 8; and wherein in each case of X is either O or C the ratio of the number of equivalents of said carboxylic acid groups, anhydride groups, or salts thereof to the number of equivalents of said hydroxyl groups is from 1/0.01 to 1/3; contacting said substrate with said curable aqueous composition or, alternatively, applying said curable aqueous composition to said substrate; and heating said curable aqueous composition at a temperature of from 100° C. to 400° C.
 9. A fibrous article, non-woven article or composite prepared by the method as claimed in claim
 8. 